Yellow-reactive monoazo dyes containing a tertiary or a quarternary nitrogen group, methods for their preparation and use thereof for dyeing hydroxy-and/or carboxamido-containing fiber material

ABSTRACT

Monoazo dyestuffs of the formula (1)  
                 
 
     wherein  
     Y is vinyl or is ethyl which is substituted in the β-position by a substituent which can be eliminated by the action of an alkali, forming the vinyl group;  
     M, X, are groups customary to dyestuffs,  
     R 1 , R 2  is hydrogen methyl, methoxy or sulfo;  
     Q is cyanamido or is a group of the formula (a) or (b)  
                 
 
     A, B, D are hydrogen, optionally substituted C 1 -C 6  alkyl or phenyl, or is alternately a group of the formula (a) or (b) wherein (a) is a cyclic ring system having a tertiary nitrogen of (b) is a cyclic having a quarternary nitrogen.  
     n is 0 if Q is a group of the formula (a) and n is 1 if Q is a group of formula (b);  
     W− is a halogenide or the equivalent of a divalent anionic group.  
     The invention further relates to the method for preparing the dyestuff and use for dyeing.

[0001] The present invention relates to the field of fiber-reactivedyes.

[0002] Yellow reactive dyes are known from U.S. Pat. No. 5,456,727, EP141367, 395951, 486176, 623655, 630946, 632107 and 647683. However thesedyes have some deficiencies, such as poor color build-up orunsatisfactory staining behaviour of the dyeings.

[0003] With the present invention, yellow dyes of improved propertiesconforming to the general formula (1) have unexpectedly been found,which produce dyeings in very good color yields with excellent colorbuild-up and consistent shade. Additionally the dyeings obtained usingthe inventive dyes surprisingly show no or very little staining onpolyamide fibers.

[0004] The present invention provides yellow dyes conforming to thegeneral formula (1)

[0005] wherein

[0006] Y is vinyl or is ethyl which is substituted in the β-position bya substituent which can be eliminated by the action of an alkali,forming the vinyl group, such as chlorine, thiosulfato, sulfato,alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphate,sulfobenzoyloxy and p-toluylsulfonyloxy, and is preferably vinyl,β-chloroethyl, β-thiosulfatoethyl or β-sulfatoethyl and is in particularvinyl or β-sulfatoethyl;

[0007] M is hydrogen or an alkali metal, such as lithium, sodium orpotassium;

[0008] X is fluorine, chlorine, amino, C₁ to C₄alkoxy, such as methoxy,ethoxy, propyloxy, butyloxy, or is phenoxy, or phenylamino, which may besubstituted by halogen or sulfo, mono- or dialkyl amine, with C₁ to C₄alkyl, such as methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl,sec-butyl, tert-butyl, which may be substituted further by sulfo,sulfato or hydroxy groups, preferably amino or methoxy or fluoro and isin particular chlorine;

[0009] R¹ is hydrogen, methyl, methoxy or a group of the formula SO₃M,preferably methoxy and in particular hydrogen;

[0010] R² has one of the meanings of R¹;

[0011] Q is cyanamido or is a group of the formula (a) or (b)

[0012] wherein

[0013] A is hydrogen, C₁ to C₆ alkyl such as methyl, ethyl, n-propyl ,i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl,preferably C₁ to C₄ alkyl groups, in particular methyl and ethyl, whichmay be substituted by hydroxy, sulfo or sulfato or is phenyl which maybe substituted by one or more halogens such as chloro, fluoro or bromo,by acetamido- or by sulfo and is preferably 4-chlorophenyl and inparticular 3-metanilic or 2,5-dimetanilic acid;

[0014] B has one of the meanings of A and is preferably hydrogen, methylor ethyl;

[0015] D has one of the meanings of A; or the group of the formula

[0016] (a) is a cyclic ringsystem such as morpholino, piperidino orpiperazino, in particular morpholino, or prolino;

[0017] (b) is a cyclic ringsystem such as N-methyl morpholinium orN-ethyl morpholinium, N-ethyl piperidinium, or is a bicyclic ringsystemsuch as 1,4-diaminobicyclo (2,2,2) octyl, or is pyridinium which may besubstituted by carboxy, such as 3-carboxy-pyridinium or4-carboxy-pyridinium, or by carboxamido, such as3-carboxamidopyridinium, and is in particular 3-carboxy-pyridinium;

[0018] n is 0 if Q is a group of the formula (a) and n is 1 if Q is agroup of formula (b);

[0019] W⁻ is a halogenide or the equivalent of a divalent anionic groupsuch as sulfate or carbonate and is preferably chloride or fluoride;

[0020] The groups “sulfo”, “thiosulfato”, “carboxy”, “phosphato” and“sulfato” include both the acid form and the salt form of these groups.Accordingly, sulfo groups are groups of the formula —SO₃M, thiosulfatogroups are groups of the formula —S—SO₃M, carboxy groups are groups ofthe formula —COOM, phosphato groups are groups of the formula —OPO₃M₂and sulfato groups are groups of the formula —OSO₃M, in which M isdefined as above.

[0021] The dyes of the general formula (1) can have, within the meaningof Y, structurally different fiber-reactive groups —SO₂—Y. Inparticular, the fiber reactive groups —SO₂—Y are partly vinylsulfonylgroups and partly groups in which Y is a β-ethyl substituted group asdefined above, such as β-chloroethylsulfonyl, β-thiosulfatoethylsulfonylor, preferably, β-sulfatoethylsulfonyl groups. If the dye contains therespective dye component in the form of a vinylsulfonyl dye, theproportion of the respective vinylsulfonyl dye to the respective dyewith Y being a β-ethyl substituted group as defined above, such as aβ-chloro- or β-thiosulfato- or β-sulfatoethyl-sulfonyl dye, will be upto about 30 mol-%, based on the respective dye chromophore. Preferenceis given to the dyes in which the proportion of vinylsulfonyl dye tosaid β-ethyl substituted dye, such as β-sulfatoethylsulfonyl dye is interms of the molar ratio between 5:95 and 30:70.

[0022] The dyes of the invention can be present as a preparation insolid or liquid (dissolved) form. In solid form they generally containthe electrolyte salts customary in the case of water-soluble and inparticular fiber-reactive dyes, such as sodium chloride, potassiumchloride and sodium sulfate, and also the assistants customary incommercial dyes, such as buffer substances capable of establishing a pHin aqueous solution between 3 and 7, such as sodium borate, sodiumbicarbonate, sodium citrate, sodium dihydrogenphosphate and disodiumhydrogenphosphate, small amounts of siccatives or, if they are presentin liquid, aqueous solution (including the presence of thickeners of thetype customary in print pastes), substances which ensure the permanenceof these preparations, for example mold preventatives.

[0023] If the dyes take the form of dye powders, they contain, as arule, 10 to 50% by weight, based on the dye powder or preparation, of astrength-standardizing colorless diluent electrolyte salt, such as thosementioned above. These dye powders may in addition contain theabovementioned buffer substances in a total amount of up to 5%, based onthe dye powder. If the dyes of the invention are present in aqueoussolution, the total dye content of these aqueous solutions is up toabout 75% by weight, the electrolyte salt content of these aqueoussolutions preferably being below 10% by weight, based on the aqueoussolutions (liquid preparations) and they can in general contain theabovementioned buffer substances in an amount of up to 10% by weight,preferably up to 5% by weight.

[0024] The dyes of the invention can be obtained in a conventionalmanner, for instance by synthesis by means of customary diazotizationand coupling reactions in a manner familiar to those skilled in the artusing appropriate substituted phenylamine derivatives conforming to thegeneral formula (2)

[0025] wherein Y is a alkali eliminable group and R¹ and R² are asdefined above, and coupling components, such as diaminophenylsulfonicacid in the necessary proportions to give the diazo component of thegeneral formula (3).

[0026] wherein R¹, R² and Y are as defined above.

[0027] Reacting this intermediate at pH 9,5-1,5 with cyanuric halogenidegives the azo dye conforming to the formula (4):

[0028] wherein X is fluorine or chlorine, and by reaction with acompound of the general formula Q′ at pH 2-9 eventually under heatingwherein Q′ is a group of the formula:

[0029] in which

[0030] A, B, D and n are as defined above to give a claimed dyestuff ofthe formula (1a):

[0031] with X, Y, W, n, Q′, R¹ and R² as defined above, and subsequentintroduction of X by substitution reaction in conventional manner if Xis different of fluorine and chlorine.

[0032] The resulting dyestuff can be isolated from the solution in theconventional manner, for example by salting out with an electrolytesalt, such as sodium chloride or potassium chloride, or by spray-drying.

[0033] Dye components in form of the vinylsulfonyl dye can be preparedby the above mentioned method using appropriate vinylsulfonyl startinganilines, or alternately by reacting the dye mixture in which Y is aβ-chloroethyl, β-thiosulfatoethyl, or β-sulfatoethyl radical with alkaliby generally known methods. Dyes in form of a vinylsulfonyl dye withinthe proportion as defined above, are synthesized upon reacting therespective dye with Y being a β-chloroethyl, β-thiosulfatoethyl,β-sulfatoethyl radical with the required amount of alkali to convertsaid β-substituted ethylsulfonyl groups into vinylsulfonyl groups in therequired proportion.

[0034] The dyes of the instant invention are well suitable for dyeing(which includes printing) hydroxy- and/or carboxamido-containing fibermaterials by the application and fixing methods numerously described inthe art for fiber-reactive dyes, in yellow shades with good colorbuild-up and good wash-off in respect of unfixed dye portions. Moreover,the dyeings obtained surprisingly show very little or no staining onpolyamide fibers.

[0035] The present invention therefore also provides for use of theinventive dyes for dyeing (including printing) hydroxy- and/orcarboxamido-containing fiber materials and processes for dyeing suchfiber materials and processes for dyeing such materials using dyesaccording to the invention by applying the dyes to the substrate indissolved form and fixing the dyes on the fiber by the action of analkali or by heating or both.

[0036] Hydroxy-containing materials are natural or synthetichydroxy-containing materials, for example cellulose fiber materials,including in the form of paper, or their regenerated products andpolyvinyl alcohols. Cellulose fiber materials are preferably cotton butalso other natural vegetable fibers, such as linen, hemp, jute and ramiefibers; regenerated cellulose fibers are for example staple viscose andfilament viscose.

[0037] Carboxamido-containing materials are for example synthetic andnatural polyamides and polyurethanes, in particular in the form offibers, for example wool and other animal hairs, silk, leather,nylon-6,6, nylon-6, nylon-11, and nylon-4.

[0038] Application of the inventive dyes is by generally known processesfor dyeing and printing fiber materials by the known applicationtechniques for fiber-reactive dyes. The inventive dyes are alsoadvantageously useful in exhaust dyeing processes. Applied in this wayfor example to cellulose fibers from a long liquor ratio at temperaturesbetween 40 and 105° C., optionally at temperatures up to 130° C., undersuperatmospheric pressure, and optionally in the presence of customarydyeing assistants with the use of acid-binding agents and optionallyneutral salts, such as sodium chloride or sodium sulfate, they producedyeings in very good color yields with excellent color build-up andconsistent shade. One possible procedure is to introduce the materialinto the warm bath, gradually heat the bath to the desired dyeingtemperature, and complete the dyeing process at that temperature. Theneutral salts which speed up the exhaustion of the dyes can also ifdesired not be added to the bath until the actual dyeing temperature hasbeen reached.

[0039] Similarly, the conventional printing processes for cellulosefibers, which can either be carried out in single-phase, for example byprinting with a print paste containing sodium bicarbonate or some otheracid-binding agent and the colorant, and subsequent steaming at from 100to 103° C., or in two phases, for example by printing with a neutral orweakly acid print paste containing the colorant and subsequent fixationeither by passing the printed material through a hotelectrolyte-containing alkaline bath or by overpadding with an alkalineelectrolyte-containing padding liquour and subsequent batching of thistreated material or subsequent steaming or subsequent treatment with dryheat, produce strong prints with well defined contours and a clear whiteground. Changing fixing conditions has only little effect on the outcomeof the prints. Not only in dyeing but also in printing the degrees offixation obtained with dyes of the invention are very high. The hot airused in dry heat fixing by the customary thermofix processes has atemperature of from 120 to 200° C. In addition to the customary steam atfrom 101 to 103° C., it is also possible to use superheated steam andhigh pressure steam at up to 160° C.

[0040] Acid-binding agents for fixing the dyes to cellulose fibers arefor example water-soluble basic salts of alkali metals and of alkalineearth metals of inorganic or organic acids, and compounds which releasealkali when hot. Of particular suitability are the alkali metalhydroxides and alkali metal salts of weak to medium inorganic or organicacids, the preferred alkali metal compounds being the sodium andpotassium compounds. These acid-binding agents are for example sodiumhydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate,potassium carbonate, sodium formate, sodium dihydrogenphosphate anddisodium hydrogenphosphate.

[0041] Treating the inventive dyes with the acid-binding agents with orwithout heating bonds the dyes chemically to the cellulose fiber;especially the dyeings on cellulose, after they have been given theusual aftertreatment of rinsing to remove unfixed dye portions, showexcellent wet fastness properties, in particular since the unfixed dyeportions are readily washed off because of their good cold watersolubility.

[0042] The dyeings of polyurethane and polyamide fibers are customarilycarried out from an acid medium. The dyebath may contain for exampleacetic acid and/or ammonium sulfate and/or acetic acid and ammoniumacetate or sodium acetate to bring it to the desired pH. To obtain adyeing of acceptable levelness it is advisable to add customary levelingassistants, for example based on a reaction product of cyanuric chloridewith three times the molar amount of an aminobenzenesulfonic acid oraminonaphthalenesulfonic acid or based on a reaction product of forexample stearylamine with ethylene oxide. In general the material to bedyed is introduced into the bath at a temperature of about 40° C. andagitated therein for some time, the dyebath is then adjusted to thedesired weakly acid, preferably weakly acetic acid, pH, and the actualdyeing is carried out at temperature between 60 and 98° C. However, thedyeings can also be carried out at the boil or at temperatures up to120° C. (under superatmospheric pressure).

[0043] The examples which follow illustrate the invention. Parts andpercentages are by weight, unless otherwise stated.

EXAMPLE 1

[0044] a. 281 parts 4-β-sulfatoethyl-anilin are suspended in 1000 partswater and 232 parts conc. hydrochloric acid are added thereto. Themixture is cooled to 0° C. and is diazotized by addition of 200 parts ofa 5 molar solution of sodium nitrite. After stirring for 1 hour at thistemperature excess nitrite is destroyed by the addition of urea.

[0045] b. 188 parts 2,4-diamino phenylsulfonic acid are dissolved in1000 parts of water at pH 7 at and the diazo solution a) is added heretoat a temperature of 0° C. Then the reaction is set to pH 5-9 and 184parts cyanuric chloride are added. The pH is held between 5 and 9 andafter completion of the reaction salt is added to precipitate the dyeintermediate which in form of the free acid has structure (A):

[0046] c . Intermediate (A) is dissolved in 1000 parts water at pH 7 and123 parts nicotinic acid are added while maintaining the pH withlithiumcarbonate in a range between 5 and 9 and a temperature of 10-60°C. Spray drying yields the lithium salt form of dye (B):

EXAMPLE 2

[0047] To one mol of dye intermediate (A) prepared as described aboveare added 112 parts 1,4-diamino bicyclo (2,2,2) octane, whilemaintaining the pH between 5-9. Drying of the dye solution yieldsdyestuff C

EXAMPLE 3

[0048] A solution of 341 parts of 2,5-dimethoxy-4-β-sulfatoethylanilineare diazotized as described in example 1a. The resulting diazo compoundis coupled as described in 1b) and the acylated with 135 parts cyanuricfluoride at pH 5-8 and 0° C. After 30 minutes morpholine is added at pH6-8 and the pH is maintained by addition of soda to afford afterspraydrying the sodium salt of dyestuff (D):

EXAMPLE 4

[0049] Treatment of the intermediate (A) with 2,5 dimetanilic acid at pH7 and room temperature in water followed by the addition of isonicotinicamide and heating at pH 7 results in the formation of dyestuff (E),which can be salted out:

EXAMPLES 5-28

[0050] Using the method described above the following dyestuffs can beprepared: Example Structure 5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

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29

I claim:
 1. Monoazodyestuff of the formula (1)

wherein Y is vinyl or is ethyl which is substituted in the β-position bya substituent which can be eliminated by the action of an alkali,forming the vinyl group; M is hydrogen or an alkali metal; X isfluorine, chlorine, amino, C₁ to C₄ alkoxy, phenoxy, unsubstitutedanilino, or anilino which is substituted by a halogen or sulfo group, amono-C₁-C₄ alkyl amino, or di-C₁ to C₄ alkyl amino, wherein said C₁ toC₄ alkyl which is optionally substituted by sulfo, sulfato or hydroxygroups; R¹ is hydrogen methyl, methoxy or sulfo; R² has one of themeanings of R¹; Q is cyanamido or is a group of the formula (a) orformula (b)

wherein A is hydrogen, unsubstituted C₁-C₆ alkyl, or C₁-C₆ alkyl whichis substituted by a hydroxy, sulfo or sulfato group or is phenyl whichis optionally substituted by one or more halogens, acetamido group, orsulfo; B has one of the meanings of A; D has one of the meanings of A oris a group of the formula (c) or formula (d) wherein formula (c) is acyclic ring system or formula (d) is a cyclic ring system, a bicyclicring system, pyridinium which is optionally substituted by carboxy orcarboxamido; n is 0 if Q is a group of the formula (a) and n is 1 if Qis a group of formula (b); W− is a halogenide or the equivalent of adivalent anionic group.
 2. The dyestuff as claimed in claim 1, wherein Xis chlorine.
 3. The dyestuff as claimed in claim 1, wherein Q is a groupof the formula (a) and wherein A is hydrogen or ethyl and B isphenylsulfonic acid.
 4. The dyestuff as claimed in claim 2, in which Qis a group of the formula (a) and wherein A is hydrogen or ethyl and Bis phenylsulfonic acid.
 5. The dyestuff as claimed in claim 3, whereinformula (c) is morpholine.
 6. The dyestuff as claimed in claim 1,wherein M is hydrogen, lithium, sodium or potassium; A is hydrogen,C₁-C₆ alkyl, or C₁-C₆ alkyl which is optionally substituted by ahydroxy, sulfo or sulfato group or is phenyl which is optionallysubstituted by one or more halogens selected from the group consistingof chloro, fluoro and bromo, by a acetamido group or by sulfo; formula(c) is morpholino, piperidino or piperazino and formula (d) isN-methylmorpholinium, N-ethyl morpholinium, N-ethyl piperidinium orN-1,4-diaminobicyclo (2,2,2) octane, unsubstituted pyridinium, orpyridinium which is substituted by carboxy or carboxamido; W′ is asulfate or carbonate.
 7. The dyestuff as claimed in claim 6, whereinformula (b) is N-1,4-diaminobicyclo (2,2,2) octane, unsubstitutedpyridinium, or pyridinium which is substituted by carboxy orcarboxamido.
 8. The dyestuff as claimed in claim 1, wherein Q ispyridinium which is substituted by carboxy or carboxamido.
 9. Thedyestuff as claimed in claim 1, wherein formula (d) is pyridinium whichis substituted by carboxy.
 10. A process for the preparation of a dye ofthe formula (1)

wherein Y is vinyl or is ethyl which is substituted in the β-position bya substituent which can be eliminated by the action of an alkali,forming the vinyl group; M is hydrogen or an alkali metal; X isfluorine, chlorine, amino, C₁ to C₄ alkoxy, phenoxy, unsubstitutedanilino, or anilino which is substituted by a halogen or sulfo group, amono-C₁ to C₄ alkyl amino, di-alkyl amino, wherein said C₁ to C₄ alkyl,is optionally substituted by sulfo, sulfato or hydroxy groups; R¹ ishydrogen methyl, methoxy or sulfo; R² has one of the meanings of R¹; Qis cyanamido or is a group of the formula (a) or formula (b)

wherein A is hydrogen, unsubstituted C₁-C₆ alkyl, or C₁-C₆ alkyl whichis substituted by a hydroxy, sulfo or sulfato group or is phenyl whichis optionally substituted by one or more halogens, acetamido group orsulfo; B has one of the meanings of A; D has one of the meanings of A oris a group of the general formula (c) or formula (d) wherein formula (c)is a cyclic ring system or formula (d) is a cyclic ring system or abicyclic ring system, pyridinium which is optionally substituted bycarboxy or carboxamido; n is 0 if Q is a group of the formula (a) and nis 1 if Q is a group of formula (b); W− is a halogenide or theequivalent of a divalent anionic group; which comprise diazotizating asubstituted phenylamine compound of the formula (2)

wherein R¹, R² and Y are as defined in claim 1, coupling onto adiaminophenlysulfonic acid, acylation of the resulting intermediate (3)

with cyanuric halogenide and subsequent reaction with a group of formulaQ′

in which A, B, D and n are as defined above, and introduction of X bysubstitution reaction, if X is different of fluorine or chlorine,wherein R¹ and R² are defined as given in claim
 1. 11. A process fordyeing hydroxy- and/or carboxamido-containing fiber material, whichcomprises applying the dyes as claimed in claim 1 to the material andfixation of the dyes to the material by means of
 1. heat
 2. with the aidof an alkali or
 3. heat and with the aid of an alkali.